A photochemical route to heterometallic complexes. Synthesis and structural characterization of Di- and trinuclear complexes having a molybdenocene or tungstenocene unit

Takayuki Nakajima, Takaya Mise, Isao Shimizu, Yasuo Wakatsuki

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Abstract

Irradiation of a mixture of tungstenocene or molybdenocene dihydride and a metal-metal-bonded dimeric complex has been found to be a convenient route to homo- and heterometallic complexes. The photoreactions of (η5-C5H5)2M1H 2 with [(η5-C5H5)M2(CO) 3]2 (M1, M2 = W, Mo) in DME afford in good yields the bimetallic complexes (η5-C5H5)(CO)M 1(μ,σ-η5-C5H4)-M 2(CO)25-C5H5) with a M1-M2 bond. (1a, M1 = W, M2 = Mo; 1b, M1 = Mo, M2 = W; 1c, M1 = M2 = W; 1d, M1 = M2 = Mo). By use of [(η5-C5R5)Ni(CO)]2 as the dimer part, the heterobimetallic hydrides (η5-C5H5) 2M(μ-H)(μ-CO)Ni(C5R5) (2a, M = W, R = H; 2b, M = W, R = Me; 2c, M = Mo, R = H, 2d, M = Mo, R = Me) were obtained, where the two metallocene cyclopentadienyl rings remain intact and the metal-metal bond is bridged by CO and hydride. Similar photolysis of a mixture of (η5-C5H5)2MH2 and [(η5-C5H5)Ru(CO)2]2 has afforded two trimetallic complexes: (η5-C5H5)(μ,σ-η 5-C5H4)M(μ-CO)2Ru(η 5-C5H5)Ru(η5-C5H 5)-(CO)H (3a, M = W; 3b, M = Mo), where the Ru-Ru bond still exists with a new M-Ru bond and one bridging (μ,σ-η5-C5H4) ring between M and the other Ru, and (μ,σ-η5-C5H4)2-MH 2[(η5-C5H5)Ru(CO)]2 (4a, M = W; 4b, M = Mo), in which both of the cyclopentadienyl rings of the metallocene are metalated with Ru. The crystal and molecular structures of 1a, 2d, 3a, and 4a have been determined by single-crystal X-ray diffraction analysis.

Original languageEnglish
Pages (from-to)5598-5604
Number of pages7
JournalOrganometallics
Volume14
Issue number12
Publication statusPublished - 1995

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Carbon Monoxide
routes
synthesis
metals
hydrides
rings
dihydrides
Metals
photolysis
molecular structure
Hydrides
dimers
crystal structure
irradiation
single crystals
diffraction
Photolysis
x rays
Dimers
X ray diffraction analysis

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

A photochemical route to heterometallic complexes. Synthesis and structural characterization of Di- and trinuclear complexes having a molybdenocene or tungstenocene unit. / Nakajima, Takayuki; Mise, Takaya; Shimizu, Isao; Wakatsuki, Yasuo.

In: Organometallics, Vol. 14, No. 12, 1995, p. 5598-5604.

Research output: Contribution to journalArticle

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abstract = "Irradiation of a mixture of tungstenocene or molybdenocene dihydride and a metal-metal-bonded dimeric complex has been found to be a convenient route to homo- and heterometallic complexes. The photoreactions of (η5-C5H5)2M1H 2 with [(η5-C5H5)M2(CO) 3]2 (M1, M2 = W, Mo) in DME afford in good yields the bimetallic complexes (η5-C5H5)(CO)M 1(μ,σ-η5-C5H4)-M 2(CO)2(η5-C5H5) with a M1-M2 bond. (1a, M1 = W, M2 = Mo; 1b, M1 = Mo, M2 = W; 1c, M1 = M2 = W; 1d, M1 = M2 = Mo). By use of [(η5-C5R5)Ni(CO)]2 as the dimer part, the heterobimetallic hydrides (η5-C5H5) 2M(μ-H)(μ-CO)Ni(C5R5) (2a, M = W, R = H; 2b, M = W, R = Me; 2c, M = Mo, R = H, 2d, M = Mo, R = Me) were obtained, where the two metallocene cyclopentadienyl rings remain intact and the metal-metal bond is bridged by CO and hydride. Similar photolysis of a mixture of (η5-C5H5)2MH2 and [(η5-C5H5)Ru(CO)2]2 has afforded two trimetallic complexes: (η5-C5H5)(μ,σ-η 5-C5H4)M(μ-CO)2Ru(η 5-C5H5)Ru(η5-C5H 5)-(CO)H (3a, M = W; 3b, M = Mo), where the Ru-Ru bond still exists with a new M-Ru bond and one bridging (μ,σ-η5-C5H4) ring between M and the other Ru, and (μ,σ-η5-C5H4)2-MH 2[(η5-C5H5)Ru(CO)]2 (4a, M = W; 4b, M = Mo), in which both of the cyclopentadienyl rings of the metallocene are metalated with Ru. The crystal and molecular structures of 1a, 2d, 3a, and 4a have been determined by single-crystal X-ray diffraction analysis.",
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T1 - A photochemical route to heterometallic complexes. Synthesis and structural characterization of Di- and trinuclear complexes having a molybdenocene or tungstenocene unit

AU - Nakajima, Takayuki

AU - Mise, Takaya

AU - Shimizu, Isao

AU - Wakatsuki, Yasuo

PY - 1995

Y1 - 1995

N2 - Irradiation of a mixture of tungstenocene or molybdenocene dihydride and a metal-metal-bonded dimeric complex has been found to be a convenient route to homo- and heterometallic complexes. The photoreactions of (η5-C5H5)2M1H 2 with [(η5-C5H5)M2(CO) 3]2 (M1, M2 = W, Mo) in DME afford in good yields the bimetallic complexes (η5-C5H5)(CO)M 1(μ,σ-η5-C5H4)-M 2(CO)2(η5-C5H5) with a M1-M2 bond. (1a, M1 = W, M2 = Mo; 1b, M1 = Mo, M2 = W; 1c, M1 = M2 = W; 1d, M1 = M2 = Mo). By use of [(η5-C5R5)Ni(CO)]2 as the dimer part, the heterobimetallic hydrides (η5-C5H5) 2M(μ-H)(μ-CO)Ni(C5R5) (2a, M = W, R = H; 2b, M = W, R = Me; 2c, M = Mo, R = H, 2d, M = Mo, R = Me) were obtained, where the two metallocene cyclopentadienyl rings remain intact and the metal-metal bond is bridged by CO and hydride. Similar photolysis of a mixture of (η5-C5H5)2MH2 and [(η5-C5H5)Ru(CO)2]2 has afforded two trimetallic complexes: (η5-C5H5)(μ,σ-η 5-C5H4)M(μ-CO)2Ru(η 5-C5H5)Ru(η5-C5H 5)-(CO)H (3a, M = W; 3b, M = Mo), where the Ru-Ru bond still exists with a new M-Ru bond and one bridging (μ,σ-η5-C5H4) ring between M and the other Ru, and (μ,σ-η5-C5H4)2-MH 2[(η5-C5H5)Ru(CO)]2 (4a, M = W; 4b, M = Mo), in which both of the cyclopentadienyl rings of the metallocene are metalated with Ru. The crystal and molecular structures of 1a, 2d, 3a, and 4a have been determined by single-crystal X-ray diffraction analysis.

AB - Irradiation of a mixture of tungstenocene or molybdenocene dihydride and a metal-metal-bonded dimeric complex has been found to be a convenient route to homo- and heterometallic complexes. The photoreactions of (η5-C5H5)2M1H 2 with [(η5-C5H5)M2(CO) 3]2 (M1, M2 = W, Mo) in DME afford in good yields the bimetallic complexes (η5-C5H5)(CO)M 1(μ,σ-η5-C5H4)-M 2(CO)2(η5-C5H5) with a M1-M2 bond. (1a, M1 = W, M2 = Mo; 1b, M1 = Mo, M2 = W; 1c, M1 = M2 = W; 1d, M1 = M2 = Mo). By use of [(η5-C5R5)Ni(CO)]2 as the dimer part, the heterobimetallic hydrides (η5-C5H5) 2M(μ-H)(μ-CO)Ni(C5R5) (2a, M = W, R = H; 2b, M = W, R = Me; 2c, M = Mo, R = H, 2d, M = Mo, R = Me) were obtained, where the two metallocene cyclopentadienyl rings remain intact and the metal-metal bond is bridged by CO and hydride. Similar photolysis of a mixture of (η5-C5H5)2MH2 and [(η5-C5H5)Ru(CO)2]2 has afforded two trimetallic complexes: (η5-C5H5)(μ,σ-η 5-C5H4)M(μ-CO)2Ru(η 5-C5H5)Ru(η5-C5H 5)-(CO)H (3a, M = W; 3b, M = Mo), where the Ru-Ru bond still exists with a new M-Ru bond and one bridging (μ,σ-η5-C5H4) ring between M and the other Ru, and (μ,σ-η5-C5H4)2-MH 2[(η5-C5H5)Ru(CO)]2 (4a, M = W; 4b, M = Mo), in which both of the cyclopentadienyl rings of the metallocene are metalated with Ru. The crystal and molecular structures of 1a, 2d, 3a, and 4a have been determined by single-crystal X-ray diffraction analysis.

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